Mineral oil composition



Patented Apr. 14, 1942 Mnnsaar. on. ooMrosrrroN Orland M. Reid and Howard D. Hartough, Woodbury. N, 3., assignors to Socony-Vacuum i! Company, Incorporated, New York, N. Y., a corporation of New York N 0 Drawing.

31 Claims.

This invention has to do in a general way with mineral oil compositions and is more particularly related to compositions comprised of mineral oil and a minor proportion of an added ingredient which will improve the oil in one or more important respects.

It is well known to those familiar with the art that mineral oil fractions refined for their various uses are in and of themselves usually deficient in one or more respects, so that their practical utility is limited even in the particular field for which they have been refined. For example, mineral oil fractions refined for use as lubricants have a tendency to oxidize under conditions of use with the formation of sludge or acidic oxidation products; also the lighter fractions such as gasoline and kerosene tend to oxidize with the formation of color bodies, gum, etc. In order to prevent the formation of these products and thereby extend the useful life of the oil fraction, it is common practice to blend with such oil fractions an additive ingredient which will have the effect of inhibiting oxidation, such ingredients being generally known to the trade as oxidation inhibitors or sludge inhibitors,;gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oil fractions for the purpose of improving "oiliness characteristics and the wearreducing action of such mineral oils when they are used as lubricants, particularly when the oils are used for the purpose of lubricating metal surfaces which are engaged under extremely high pressures and at high rubbing speeds.

Other ingredients have been developed for the purpose of depressing the pour point of mineral oil fractions which have been refined for use as lubricants, such refinement leaving a certain amount of wax in the oil, which, without the added ingredient, would tend to crystallize at temperatures which would render the oil impracticable for use under low temperature conditions. Additive agents have also.been developed for improving the viscosity index of lubricating oil fractions. In the case of internal combustion, engines, particularly those operating with high cylinder pressures, there is a decided tendency for the ordinary lubricating oil frac-.- tions to form, under such conditions of use, carbonaceousdeposits which cause the piston rings to become stuck in their slots and which fill the slots in the oil ring or rings, thus materially reducing the efficiency of the engine. Ingredients have therefore been developed which, when add- Application February 3, 1940, Serial No. 317,122

Aside from the corrosive action which attends the formation of acidic products of oxidation in ed to the oil, will reduce the natural tendency '55 mineral oil fractions of the lubricant range, it has been discovered that certain types of recently developed hard metal alloy bearing metals, such as cadmium-silver alloy bearings, are attacked by ingredients in certain types of oils, particularly oils of high viscosity index obtained by various methods of solvent-refining. This corrosive action on alloys of the above type has led to the development'of corrosion inhibitors which may be used in solvent-refined oils to protect such bearing metals against this corrosive action.

Inthe lighter mineral oil fractions, such as those used for fuel purposes, particularly in internal combustion engines, it has beenfound that the combustion characteristics of the fuel may be controlled and improved by adding minor proportions of various improving agents thereto.

The various ingredients which have been developed for use in mineral oil fractions to improve such fractions in the various respects enumerated above are largely specific to their particular applications, and it has therefore been the practice to add a separate ingredient for each of the improvements which is to be effected.

It is a primary object of the present invention to provide a mineral oil composition which has been improved in one or more of' the various properties enumerated above by the incorporation therein of a small quantity of a multifunctional compound selected from that group or class of metal-organic compounds which is herein referred to generically as the oil-soluble or oil-miscible nuclear alkyl-substituted amino aryl metal oxides or nuclear alkyl-substituted amino phenates, the terms amino and phenates being used in their broadest generic sense, that is to say the term amino" includes both sub-= stituted ,and unsubstituted NHz groups (preferably a metal-substituted NH: group wherein an H of the NHz group has been substituted by a metal, such group being hereinafter referred to as a metal amino group) and the term phenates includes both monoand poly-cyclic hydroxyaromatic compounds in which the hydrogen of a hydroxy group has been substituted by a metal. These oil-miscible nuclear'alkyl-substituted amino aryl metal oxides should, of course, be substantially stable toward the mineral oils when intimately admixed therewith.

We have discovered that amino aryl ,metal oxides or amino phenates of the generic class above referred to may be added in small quantities to mineral'oil fractions to form mineral oil compositions or blends superior to the unblended fractions in one or more important respects, and the present invention, therefore, is broadly directed to a mineral oil composition containing a compound falling into the general class referred to.

The oil-improving agents contemplated by this invention are all characterized by the presence of an aromatic nucleus in which at least one nuclear hydrogen has been substituted with an hydroxyl group, the hydroxyl hydrogen of which is replaced with its equivalent weight of metal and in which another nuclear hydrogen has been substituted with a radical selected from the group consisting of amino, alkyl-amino, aralkyl-amino, acyl-amino and metal-amino radicals or groups. This characterizing group may be represented by the formula:

T(OM) (N) in which T represents an aromatic nucleus; (0M) represents at least one hydroxyl group in which hydrogen is replaced with its equivalent weight of metal, M; and (N) represents a nitrogen-containing radical selected from the group consisting of amino, alkyl-amino, aralkyl-amino, acyl-amino and metal-amino radicals or groups, the (OM) group and the (N) group each being attached to the nucleus (T) The amino-aryl-metal-oxides corresponding ti the group represented by the above formula, in which the nitrogen-containing radical (N) contains only hydrogen or metal and which are otherwise unsubstituted are not miscible with mineral oil, and it is therefore important that the improving agents containing the above characterizing group have additional nuclear or an amino hydrogen, or both, re laced with substituents of an oil-solubilizing ature. Preference is given to compounds of the above type in which at least one nuclear hydrogen has been replaced with an oil-solubilizing substituent since such compounds also impart or tend to impart multifunctional properties to the compound when mixed with refined petroleum distillates. By the terms oil-miscible" or oil-soluble as they are used herein wehave reference to that property of remaining uniformly dispersed in the mineral oil fraction either as a true solution or as a colloidal suspension: during normal conditions of handling and use.

The improving agents contemplated by this invention are characterized by the presence of alkyl substituents or aliphatic radicals in the aryl nucleus, and the improving agents preferred for use in viscous mineral oils are further characterized by the presence of alkyl or aliphatic substituents in the aryl nucleus which will give other properties to the composition as a whole in addition to oil-miscibility. We have found, for example, that where the aryl nucleus is substituted with one or more aliphatic groups corresponding to certain aliphatic hydrocarbon compounds of relatively high molecular weight (herein referred to as heavy alkyl groups), a compound or composition can be obtained which will effect marked improvement in the viscosity index and the pour point as well as other important properties of this invention are nuclear alkyl-substituted groups.

aminoor substituted amino aryl metal oxides, herein termed C-alkyl-amino-phenates, having the characterizing group T(OM) (N) described above, in which additional nuclear hydrogen is replaced with an oil-solubilizing substituent such as a predominantly aliphatic material, such substituent comprising a. sufficient proportion of the composition as a whole to render the same miscible with mineral oil fractions under normal conditions of handling and use. As a further generalization it may be said that at least one I point on the aromatic nucleus T, and preferably two or more points on such nucleus, are substituted with aliphatic hydrocarbon radicals or groups, such aliphatic radicalsor groups preferably being high molecular weight derivatives or heavy alkyl groups.

The simplest type of compound satisfying the above preferred requisites may be represented by the formula:

in which R represents at least one aliphatichydrocarbon radical orgroup, such group or groups preferably corresponding to relatively high molecular weight aliphatic hydrocarbons and being attached to a monoor poly-cyclic aromatic nucleus T and in which (OM) and (N) are as indicated above, the (N) groupbeing preferably a metal amino group.

As indicated above, the preferred type of compounds contemplated by the present invention are those represented by Formula I in which the group represented by R is an aliphatic hydrocarbon radical of relatively high molecular weight, preferably containing not less than 20. carbon atoms and in which the substituent represented by (N) is a metal amino group, the latter type of compounds being hereinafter referred to as metal aminates or simply as aminates. We have found that the latter type of compounds or aminates possess greater stability toward both oxidation and water-washing under normal conditions of handling and use, than the corresponding amino compounds in which the H of the NH:

group is unsubstituted or is substituted with non metallic radicals or groups and therefore are ,much preferable to the latter under most circumstances. As also previously indicated, the compounds in which the group represented by R is a heavy aliphatic hydrocarbon radical, are preferred because of their greater oil solubility and also because such heavy aliphatic hydrocarbon radicals possess multi-functional activity when combined with mineral oils, particularly lubricating oils.

In addition to the aliphatic or alkyl substituent R, the compounds or compositions contemplated herein as mineral oil improving agents may have additional nuclear hydrogen replaced with other substituents which may or. may not have a solubilizing effect upon the composition as a whole. form may be represented by the formula:

in which R, T, and (OM) and (N) have the same significance indicated above' and in which Y represents residual hydrogen which may be replaced by a radical selected from the group consisting of: hydroxy, ch orine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, amino, keto, nitroso, diazo, azo, ether alcohol and ester radicals or Compounds of the above general for- Such a compound in its simplest I nuclei are illustrated by the following specific formulae to four, the number of aromatic nuclei T in the moleculemay likewise vary from one to four. It

will be seen, therefore, that the relationship be- R! R! R! in which (M) and (N') have-the same significance indicated above and at least one R 'improving agent, part or all of the aliphatic hydrocarbon material may be comprised of polyvalent aliphatic hydrocarbon radicals or groups in which the several valences are attached to separate aromatic nuclear groups. Compounds of this type are included under the following general formula representation:

III R"(T(OM) (N')Yb)n in which T and (OM) and (N') have the same significance indicated above; R represents at least one aliphatic or alkyl radical or group, such alkyl group or groups being attached by one valence only to at least one aromatic nucleus T, 1) representing the valence of the aliphatic radical R which may be one to four; Y?) represents a monovalent element or group selected from the class identified above in connection with Y; b represents the number of Y's and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R", (0M) or (N') and n represents a whole number from one to four and indicates the total number of groups (T(OM) (N)Yb) present in the molecule represented by the formula which are attached to the aliphatic group or groups represented by R" through the valences o.

In the foregoing general formula representation III it will be seen that the compounds represented thereby include those materials in'which all of the nuclear aliphatic substituent is monovalent (0:1 and n=l) or in which all of the aliphatic substituent is polyvalent (v and n being equal to two, three, or four) or since R is defined as being at least one aliphatic radical or group and may therefore include several such groups, it will be seen that this general Formula III is inclusive of compounds having nuclear aliphatic groups or radicals of difierent valences (from one to four) in the same molecule. Also it will be observed that since n may be any whole number from one tween 11. and o in Formula III, in its broadest aspect, is such that when n is equal to one, 1) is equal to one; and when n is greater than one, the valence v of at least one of the His is equal to n (in order to tie the several nuclei or Ts together) the valence of any remaining R's being any whole number equal to or less than 11.

As stated above, and as will appear more fully later from the description of their synthesis, these materials represented by general Formula III may contain both monovalent and polyvalent aliphatic substituents in the nucleus," Both the polyvalent aliphatic substituent and the monovalent substituent, if both are present, may be introduced in the nucleus as part of an alkylation reaction, or all or part of the monovalent aliphatic substituent may be present in the nucleus of a hydroxyaromatic starting material as low molecular weight aliphatic groups, such as methyl, ethyl, propyl groups, etc.

Compounds of .the general type last described above, which include polyvalent substituted aliphatic substituents and may also include both the monovalent and the polyvalent aliphatic substituents, are included under the sub-generic formula representation.

in which T, (OM) and (N') have the same significance as indicated above; R represents at least one polyvalent aliphatic radical or group having a valence v of two, three, or four; Yb' indicates the same group of substituents as described above for Y; R0 represents monovalent aliphatic radicals or groups; b represents the number of Ybs and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R (0M) (N') and Re; 0 indicates the number of Rc'S and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R', (OM), (N') and Yb; and N represents a whole number from two to four and indicates the total number of the groups (T(OM) (N)Yb'Re) present in. the molecule represented by the formula which are attached to the aliphatic group or groups represented by R" through the valences o.

In the above general Formulae III and IV it will be understood that since R and R" are aliphatic hydrocarbon radicals of the chain type and are each attached by one valence only to each corresponding aromatic nucleus, the valence v or v of such radical or radicals is of necessity never greater than the number n, which indicates the number of aromatic nuclei in the molecule and in Formula III is always equal to one when n equals one. Otherwise an R. or R" having a valence greater than the number (n or n) of aromatic nuclei would either have some of its valences unsatisfied or else would form a condensed ring or rings. by attachment at two or more point to one and the same aromatic nucleus. Such latter compounds, as already indicated from the definition of R or R are not considered as characterizing the product of the present invention although probably formed in some instances in minor amounts as unobjectionable by-products by certain of the methods of preparation herein disclosed.

A simple type of compound coming under general Formula III in which 17 and n is equal to one and in which there is only one oil-solubilizing aliphatic group, R", may be illustrated by the following formula showing T, for purposes, of illustration, as a monocyclic nucleus:

' 3 t n A 11" H.

In the above formula the chain represents the oil-solubilizing alkyl substituent (R and Yb, N and (OM) have the same significance as has been heretofore given to these groups.

Since group R has been defined as at least one,"'it will be apparent that there maybe more than one heavy alkyl substituent attached to the nucleus T, such a compound, where band 12. are each one and in which there are two such monovalent R groups, may be represented by' the following formula:

OM N

H H H H B HC -ofc -CH H H H in which the chains and the substituent characters have the same significance defined above. Compounds of the type satisfying the general Formula III and the sub-generic Formula IV in which R (or R is polyvalent and v (or v) and n (or n) are more than one and in which there is only one such polyvalent R group, may be illustrated by the following formula, in which the aryl nucleus T is again indicated for illustration as being monocyclic:

OM OM 0M c Yb--L;-N' Yt- -N' Yb -N R R. R. a H H H H H under Formula C:

H H H H H n c --c ----0-- ----o-- an H 0 o H IlC---.-C --0 o -CH The probable molecular structure of compounds in which the aryl nucleus T is polycyclic will be obvious from the foregoing exemplary Formulae A to, D inclusive, and the molecular structure of compounds in which '0 and n are equal to two and four will be readily understood from the exemplary Formulae C and D.

Another possible molecular structure of compounds coming under Formula III is a compound having more than one polyvalent R", at least two of which have different valences. Such a. compound may be typified by the following formula in which the symbols have the same significance as in Formula C:

As to the possible number of R (and Re) groups going to make up a single molecule, this will vary with the extent to which it is desired to effect substitution of the nucleus with oilsolubilizing aliphatic groups for obtaining the desired properties in the product and is, of course, limited by the number-of valences on the aromatic nucleus whichare available for substitution. As will be apparent to those skilled in the art, the maximum possible number of R (and Re) groups which can be attached to a single aromatic nucleus will vary as the nucleus is monoor polycyclic and also as the. nucleus is otherwise substituted. It will also be apparent that available valences on the nuclei may all be attached to polyvalent aliphatic substituents.

It will be understood that the oil-improving agents contemplated by this invention may be pure compounds satisfying the general Formula III described above with any one of-the'vari'ous mono and poly cyclic aromatic nuclei as T and the various substituents R", (N) and Y described, the only requisites being that at least one nuclear hydrogen be substituted with an amino or nitrogen containing radical N', another nuclear hydrogen being substituted with a metal-oxy group or hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of a metal and at least one nuclear hydrogen be sub-- stituted with an oil-solubilizing aliphatic radical or group. However, in manufacturing the preferred oil-improving product of the present invention by the preferred method of procedure, as will appear more fully later on, the final oilimproving product obtained is normally or usually a mixture of different compounds corresponding to different values of n and v and to difierent numbers of aliphatic groups R".

As has been emphasized hereinabove, it is important that the preferred oil-improving agents as'represented by general Formulae III and IV have nuclear hydrogen in'the aromatic nucleus T substituted with predominantly aliphatic material which comprises a suflicient proportion of the composition as a whole, particularly when N contains no, aliphatic hydrocarbon radical, to render the same miscible with the mineral oil fraction in which the improving agent is used under normal conditions of handling and use. It appears from the results of our research that there is a critical range in the degree of alkylation of these improving agents below which the product or agent will not satisfy the requirements for oil-miscibility. Expressing this in another way, it appears that the hydroxyaromatic constituent from which the metal oxide is derived should not exceed a certain percentage of such alkylated hydroxyaromatic composition'as a whole. This critical range of alkylation may be roughly expressed as the ratio by weight of (T(OH) )11. to R (T(OH) )1:-

The degree of alkylation and the critical range .within' which operative or preferred compounds can be obtained may also be expressed as the number of carbon atoms contained in the aliphatic substituents for each aryl nucleus in a given molecule or molecular structure.

The critical range in the degree of alkylation, as defined above, of the aryl nucleus in the improving agents contemplated herein may vary with: (a) the mineral oil fraction in which the improving agent is to be used; (b) the aryl nu-.

cleus T (monoor poly-cyclic) (c) the hydroxyl content of the aryl nucleus from which the metal oxide is derived (monoor poly-hydric) (d) the character of aliphatic material comprising the substituent (straight or branched chain); (c) monoor poly-substitution of the aryl nucleus; and (f) other substituents on the nucleus T, which may be of positive or negative or of neutral sclubilizing activity. I

In general it may be said that a polycyclic nucleus appears to require a higher degree of alkylation than a mono-cyclic nucleus; that a polyhydric nucleus requires a higher degree of alkylation than a monohydric nucleus; and that branched chain aliphatic substituents -have a somewhat greater solubilizing action than straight chain solubilizing substituents.

In view of the foregoing variables it would be impracticable and probably misleading to at tempt to give an expression and figure which would indicate accurately the proper ratio of hydroxyaromatic constituent to the alkylated hydroxyaromatic constituent which would express a degree of aliphatic substitution satisfying all cases taking these variables into account.

As a guide for preparing these improving agents, however, our research indicates that for a product having pour depressing and V. I. improving properties in addition to other valuable properties the ratio, expressed as:

should not be greater than 0.17 when the weight of the hydroxyaromatic nucleus or component (T(OH) )n is expressed in terms of its chemically equivalent weight of phenol (CeHsOI-I). However, for mere oil-solubility with inhibition of oxidation we have found that this ratio may be raised as high as .60 or even higher by substituting the nucleus with branched chain aliphatic groups or by including an aliphatic hydrocarbon radical in the N group. In general it may be said that in the preferred improving agents contemplated herein the ratio by weight of the hydroxyaromatic component in the product to the corresponding alkylatecl hydroxyaromatic nucleus or component therein should not be greater than about seventeen parts by weight of the former to about 100 parts by weight of the latter, or about seventeen per cent, when the weight of the hydroxyaromatic nucleus or component is expressed in terms of its chemically equivalent weight of phenol. It will be observed that the ratio as represented by the Formula VII above does not take into account any other substituent in the nucleus than the aliphatic substituents and the hydroxyl group; but since the aliphatic substituent is primarily relied upon in the agents contemplated herein as the solubilizing and multifunctional-producing substituent, itis believed that the foregoing expression and limits will serve as a working guide for the preparation of oil-soluble materials and the preferred multifunctional materials.

As stated above, the degree of alkylation may also be expressed by the number of carbon atoms contained in the aliphatic substituent for a given hydroxyaromatic nucleus T. As a general guide here it may be said that the aliphatic substituents represented by R in the above general Formula III should, for the preferred multifunctional materials contemplated herein, contain at least thirty carbon atoms for each aromatic nucleus T. The above limit is representative of preferred materials, but metal phenates which are oil-soluble and which have oxidation inhibiting action when admixed with oils have been prepared from tertiary amyl phenol which it will be observed is mono-substituted with a branched chain hydrocarbon and has only five carbon atoms in the alkyl substituents.

The ratio of seventeen per cent, which we may term the phenolic ratio, represents what we consider a maximum figure for the preferred products contemplated herein, and in general it will be found that this figure will be lower, the actual ratio, of course, being dependent upon the variable factors enumerated above. For example, as will later appear, an improving agent of the preferred type in which the aliphatic substituent in the aryl nucleus is derived from petroleum wax (a predominantly straight chain aliphatic hydrocarbon of at least twenty carbon atoms) and in which the aromatic nucleus was derived from phenol otherwise unsubstituted may have a phenolic ratio, as expressed above, not substantially greater than about thirteen per cent.

A further general guide for the synthesis of the preferred improving agents for viscous oils is to alkylate the aromatic nucleus so it is polysubstituted with aliphatic hydrocarbon radicals or groups preferably of relatively high molecular weight.

As has been previously indicated, it is one of the primary objects of the invention to provide an oil-improving agent which will have multifunctional improving activity in a mineral oil. Our research indicates that compounds satisfying the requisites of general Formula III above may be blended in minor proportions with mineral oil fractions, particularly of the viscous or lubricating oil type, to effect marked improvement in several important properties. The improvement effected may be varied somewhat by varying the character of the aliphatic substituent in the aryl nucleus, petroleum wax and aliphatic hydrocarbons of similar characteristics such as ester wax, for example, giving products which effect a marked improvement in viscosity index and pour point in addition to other properties to be hereinafter pointed out. The effectiveness may also be varied with other substituents in the aryl nucleus-for example, alkoxy and especially alkyl-amino groups may contribute to solubilityand the properties of the agents may 0 also be varied with the character of the metal substituent in the hydroxy group. In general it appears that the salt (phenate type) of any metal satisfying the requisites of Formula III above will act to inhibit oxidation in mineral oils and reduce the formation of harmful oxidation products. Certain of the metals, such, for example, as lead and zinc, may serve to increase the load-carrying capacity of lubricating oils.

The procedure whereby the oil-improving agents contemplated herein can be prepared may be broadly described as involving the substitution of the hydroxyl hydrogen in a nuclear-alkylated aminohydroxyaromatic compound with a. metal and may be indicated by the following general equation:

. wherein is an amino group wherein .1: represents residual hydrogen which may be replaced by a radical selected from the group consisting of alkyl, aralkyl and ester (acyl) groups, the remaining characters having the same significance as above. This substitution may be effected in various ways, some of which will be described hereinafter with specific examples.

It will be understood, of course, that since M r is defined as a hydrogen equivalentof a metal and since furthermore an (OH) group is more acidic than an amino group containing replaceable hydrogen, the metal will first replace the hydrogen in the (OH) group or groups before replacing any replaceable hydrogenwhich may be present in the group Therefore, in order to form an (N') group congroup, beryllium, magnesium, calcium, strontium,

and barium; the metals zinc, cadmium and mercury, scandium, yttrium, lanthanum; aluminum, gallium, indium, thallium, titanium, zirconium, cerium, thorium; germanium, tin and lead; vanadium, columbium and tantalum; arsenic, antimony and bismuth; chromium, molybdenum,

tungsten anduranium; rhenium, manganese,

iron, cobalt and nickel; ruthenium, rhodium and palladium; osmium, iridium and platinum.

Some of the rare-earth metals are given in the above; other rare earth metals suitable for the formation of amino-phenol salts are those now commercially available as the cerium and yttrium groups, namely, a mixture of prassodymium, neodymium, Samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thullium and lutecium.

The general reaction described and illustrated above has shown an alkylated or an aliphatic substituted hydroxyaromatic compound as the starting material. Compounds of this nature,

, which satisfy the requirements of highalkylation for the preferred improving agents discussed above, or mixtures of such compounds can be readily prepared by alkylating a monoor polycyclic, monoor pol'y-hydric, substituted or unsubstituted hydroxyaromatic compound with al The starting material for the hydroxyaromatic constituent in the alkylation reaction to obtain an alkylated hydroxyaromatic product in which Yb, if present, is residual hydrogen, may be a mono or poly cyclic hydroxyaromatic compound otherwise unsubstituted; or such compounds containing alkyl substituents; or in certain special cases (to be hereinafter described) the starting material may be an alkyl-aryl ether or an aralkyl-aryl ether. For obtaining an alkylated hydroxyaromatic product containing a Y substituent, in addition toor in place of residual hydrogen, the starting material for the hydroxyaromatic constituent may. be a monoor poly-cyclic hydroxyaromatic compound in which part of the nuclear hydrogen is substituted with a member or members of the group consisting of chlorine, hydroxy, alkoxy, aroxy, aryl, alkaryl, and aralkyl groups.

Examples of the hydroxyaromatic compounds which may be used as starting material for the alkylation reaction are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenyl-ethyl-phenol, phenol resins, methylhydroxydiphenyl, guaiacol, alphaand beta-naphthol, methyl alphaand methyl beta-naphthol, tolyl naphthol, xylyl naphthol, benzyl naphthol, anthranol, phenyl methyl naphthol, phenanthrol, monomethyl ether of catechol, methoxy phenol, phenoxy phenol, anisole, beta-naphthyl methyl ether, chlorphenol, and the like. Preference in' general is to the monohydroxyphenols otherwise unsubstituted,

, particular preference being given to phenols and alphaand beta-naphthol.

The alkylation of the hydroxyaromatic compound may be accomplished in various ways, such as by a Friedel-Crafts synthesis, using a halogenated aliphatic hydrocarbon, .or by reaction with unsaturated high molecular weight aliphatic compounds or higher alcohols in the presence of H2804 as a. catalyst.

We have found the Friedel-Crafts type of alkylation reaction to be particularly adapted to the step of preparing the alkylated hydroxyaromatic compounds from which the improving agents described herein are synthesized because it affords a convenient means of controlling the degree of alkylation and obtaining the desired phenolic ratio for use in the preferred mineral oil composition contemplated by this invention.

In this reaction an appropriate monoor polychlorine-substituted aliphatic compound or material is reacted with the desired hydroxyaromatic compound in the presence of a catalytic amount of aluminum chloride. tially pure monoor poly-chlorine-substituted aliphatic compounds may be used. However, as will be readily understood by those skilled in the art, since it is usually very difilcult to prepare or obtain high molecular weight aliphatic hydrocarbons in a pure or substantially pure state and since it is equally difiicult to prepare the chlorine (or other halogen) substitution products of such hydrocarbons in a pure or substantially pure state, we prefer to employ a mixture of such hydrocarbons, such as a suitable petroleum fraction, as the starting material for my preferred improving agents, converting it into a mixture' of different chlorine (or other halide) substitu- Pure or substantion products by any suitable method for use in the alkylation step. In general it may be said that the high molecular weight aliphatic hydrocarbons contemplated by this invention as preferred sources for the alkyl or aliphatic substituent R in Formula III above may be pure or mixed compounds typified by those which char-- acterize the heavier products of petroleum, such as heavy petroleum oils of the lubricant type, petrolatum and crystalline petroleum wax or other compounds or materials which will result in relatively long chain aliphatic substituents. Special preference is given to petroleum wax of melting point not substantially less than about 120 F. Such specially preferred aliphatic hydrocarbon materials commonly have molecular weights of about 250 and have at least twenty carbon atoms in their molecules.

' As stated above, the Friedel-Crafts synthesis affords a convenient means of controlling the degree of alkylation of the product. This accomplished by controlling: (a) the chlorination of the aliphatic hydrocarbon and (b) the reacting proportions of the chlorinated aliphatic hydrocarbon and the hydroxyaromatic compound used in the Friedel-Crafts reaction. As is well known to those skilled in the art, the replacement of nuclear hydrogen in the hydroxyaromatic compound with an aliphatic group is, in the Friedel-Crafts synthesis, effected by reaction of such nuclear hydrogen with chlorine in the chlorinated aliphatic compound, the substitution being effected with evolution of HCl. It will thus be seen that the number of chlorine substituents in a chlorinated aliphatic compound corresponds 3 to the number of valences (v in general Formula III) which will be satisfied by or attached to hydroxyaromatic nuclei in the product of the reaction. For example, in a reaction where a quantity of pure monochloraliphatic hydrocarbon containing say three atomic proportions of chlorine is reacted with one molecular proportion .of hydroxyaromatic compound, the resulting alkylated product corresponding to the constituent represented by R (T(o'H)Yb)n in general Formula III is one in which 11 and n are equal to one and there are three aliphatic groups R attached to one nucleus T. On the other hand, assuming a reaction in which a quantity of pure trichloraliphatic hydrocarbon containing three atomic proportions of chlorine is reacted with one molecular proportion of hydroxyaromatic compound, the product would be one in which 0 and n of general Formula III are each equal to three, and the solubilizing action of a single aliphatic group would be distributed among three nuclear hydroxyaromatic groups. It is due to this latter condition that we consider it preferable that the number of valences v (in R of Formulae HI, etc.) be maintained within the range of from one to four hereinabove specified. In other words, it appears that the required oil-solubilizing and oil-improving action of the aliphatic substituent R", particularly where the agent is to be used for multifunctional activity in viscous oils, is not obtained with materials predominantly comprised of a compound or compounds corresponding to the constituent represented by R (T(oH)Yb)n in Formula III in which 0 and n are greater than four. Hence, for use in the Friedel-Crafts reaction the chlorinated high molecular weight aliphatic material should be a compound, orshould be predominantly comprised of compounds, in

which the chlorine content is not greater than a tetrachlor compound.

As will be readily apparent to those skilled in the art, the chlorination of an aliphatic material such as a liquid petroleum fraction or a crystalline petroleum wax will normally or usually result in a. mixture of monoand poly-chlor-aliphatic hydrocarbon compounds. Consequently, the product of a Frledel-Crafts reaction between such chlorinated material and a hydroxyaromatic compoundwill be a mixture of different comounds corresponding to different values of v and n in the formula R (T(oH)Yb)n and the final metal oxide derived therefrom according to the reaction of Equation (a) above will likewise be a mixture of compounds corresponding to different values of n and v in the constituent represented by. R (T(OH)Yb)n in general Formula It will be understood, therefore, thatthe specific values for o and n in the above formula, as well as the formula itself, relate to the different specific compounds present in such a mixture which characterize it as a product of the present invention.

However, in the case of a pure compound corresponding to general Formula III or in mixtures thereof, we have, as previously stated, discovered that for a satisfactory product, the ratio by weight of hydroxyaromatic component (T(OI-I) n to the corresponding alkylated hydroxyaromatic nucleus or component (R (T(OH) )n) .shouid not be greater than a certain critical-maximum ratio which varies with constituents, conditions of use,

and properties desired, as discussed in detail hereinabove.

The above-mentioned ratio of hydroxyaromatic component to the corresponding alkylated hydroxyaromatic component,

culated as phenol and which is therefore herein referred to as the phenol content or phenolic ratio, is usually calculated from the weight of the hydroxyaromatic compound used up in the alkylation reaction and from the total weight of alkylated compound resulting from such alkylation reaction, as will b readily understood by those skilled in the art.

For example, when the Friedel-Crafts synthesis is used for alkylation, the aliphatic hydrocarbon material is first chlorinated until the weight of chlorine absorbed indicates that the average composition of the chlorinated product corresponds roughly to a dichlor-aiiphatic hydrocarbon. Such a product will, of course, contain some mono and tri-chlor compounds and probably some tetrachior compounds. The reacting proportions (based on atomic proportions of chlorine to one mole of hydroxyaromatic compound) are then selected so that the theoretical product of the Friedel-Crafts reaction will give the approximate phenolic ratio desired. After the Friedel-Crafts reaction and purification of the product the we ght of aliphatic material in the chlorinated aliphatic starting material is subtracted from the weight of the alkylated or aliphatic substituted product to obtain the weight of hydroxyaromatic material ((T(OH) )n) actually combined or used up in the alkylation synthesis. From this value and the weight of the alkylated product (R"(T(OH) 1|.) the phenolic ratio or phenol content can be readily calculated. If there are other substitucnts (Yb) on the hydroxyaromatic nucleus in addition to the monoor poly-valent aliphatic groups, a deduction should be made for them before calculating the phenolic ratio, an operation which will be apparent to those skilled in the art.

In the foregoing description of the Friedel- Crafts alkylation reaction we have referred to a hydroxyaromatic compound as a starting material. This same reaction may be used with an alkyl-aryl ether or an aralkyl-aryl ether which undergoes a substantial rearrangement during Friedel-Crafts alkylation to form an alkylated hydroxyaromatic compound in which the alkyl group of the ether replaces one of the nuclear hydrogen atoms.

In the event it is desired to obtain a product R (T(OM)Yb)n which contains an alkoxy group as the substituent Yb, it is preferable that the alkylation be efiected with a hydroxyaromatic compound containing such alkoxy or aroxy group as a substituent and a high molecular weight unsaturated aliphatic hydrocarbon (such as polymerized isobut'ylene, dodecylene, tetradecylene, octadecylene, melene, etc.) or a higher alcohol (such as cetyl alcohol, myricyl alcohol, ceryl alcohol, etc.) using H2804 as a catalyst. By this procedure, the hydroxyaromatic ether can be alkylated, without substantial rearrangement taking place. As an alternative procedure, polyhydric phenols can be nuclear alkylated by reaction with alcohols or unsaturates or by Friedel- Crafts reaction followed by substitution of the hydroxyl hydrogen of one hydroxy with a low molecular weight alkyl group. In carrying out this latter procedure, alkylated polyhydric phenol is treated with an alkali alcoholate to introduce alkali metal into the OH group followed by treating with the desired alkyl halide, whereby the substitution is effected. v

When it is desired to obtain a keto group as the Yb in general Formula III, the alkylated hydroxyaromatic compound is reacted with an aliphatic or aromatic acid anhydride in the presence of aluminum chloride as catalyst to effect the substitution before nitrating the compound. The substitution may also be carried out by reacting the alkylated hydroxyaromatic compound with an aliphatic or aromatic acid chloride, whereby the ester group is formed, followed by rearrangement of the acyl group to the nucleus. To cause this rearrangement, sufiicient AlCIs must be used as catalyst.

Nuclear Yb substituents such as nitroso, diazo, azo, ester, alkoxy. and ether-alcohol groups are introduced after the nitration and reduction reaction -by methods well-known to those skilled in the art.

A nitro group can be introduced by dinitrating the alkylated hydroxyaromatic compound, followed by selective reduction of only one nitro group, such as can be carried out by the ammonium sulfide method of reduction,

NITRATION OF ALKYLATED HYDROXYARO- MA'I'IC COMPOUNDS Theabove mentioned alkylated starting ma terialmay be readily converted, into the corresponding amino-hydroxyaromatic compound, in accordance with the preferred method, by nitration, to introduce a nitro group into the nucleus, followed by reduction of the nitro group to an unsubstituted amino group which may then be tion) with the various other substitucnts reprefl sented by a: in the group -x (u) of general formula,

R"(T(OH) :1) m.

shown in general Equation (a) above. The nitration procedure may be carried out as illustrated by the following example:

EXAMPLE I REACTION MIXTURE t-Amyl phenol (hydroxy-benzene) mol 1 enzol litre HNOa (17.5% by weight H2O, l part HNO3,

3 parts H2O) mols 2 Procedure The tert. amyl phenol is dissolved in the benzol and the nitric acid solution added slowly at room 'temperature at such a rate that the temperature rises to 130-140 F. and is maintained there throughout the remainder of the addition. After addition of the nitric acid is complete, this temperature is maintained for hour. The material is then water-washed until free of acid and the benzol removed by distillation.

REDUCTION OF ALKYLATED NITROHY- DROXYAROMATIC COMPOUNDS EXAMPLE II p-Tertfamyl nitrophenol mols l Tin metal do 3 Cone. hydrochloric acid litres 1.5

. The amyl nitrophenol and the tin are mixed together, thereafter adding the' HCl in 250 cc. portions with stirring over a periof of one hour.

The reaction temperature is then raised .to the boiling point and the mixture refluxed until all the reaction mixture until a permanent cloudiness appears, whereupon the material is set aside to cool. The compound obtained as the hydrochloride is a white to light yellow crystalline product.

Due to the susceptibility of alkylated aminohydroxyaromatic compounds to oxidation in the air'it has been advisable to store them in the form of the hydrochloride. Where it is desired to obtain the corresponding basic compound free,

the proper amount of the hydrochloride is added substituted by alkylation or acylation (esterificato a non-aqueous solvent and neutralized with ammonia gas. alkylated amino-hydroxyaromatic compound can be made in mineral oil in this manner.

PREPARATION OF NUCLEAR ALKYLATED AMINOHYDROXYAROMATIC COM- POUNDS WHEREIN AMINO HYDROGEN IS SUBSTITUTED BY AN ALKYL, ARALKYL OR. ESTER (ACYL) GROUP When nuclear alkylated, the amino-hydroxyaromatic compounds may also be N-substituted with various groups such as alkyl, aralkyl or A concentrated blend of the free hydroxystearic acid, tartaric acid, slycoliic acid,

N-Substitution with alkyl or aralkyl groups The alkylation of the amino group may be carried out by treating the amino with alkyl or aralkyl halide according to known methods.

N-Esteriflcation (acylation) with ester (acyl) groups The amino-hydroxyaromatic compounds can be esterified by treatment with an acid anhydride, organic or inorganic acyl chloride, with substitution of an amino (and in some instances of both amino and hydroxyl) hydrogen taking place.

In the esteriflcation reaction with organic acids, it is not desirable to substitute more than one amino hydrogen when metal derivatives are to be prepared. When an inorganic acyl chloride corresponding to the acid of a non-metallic or more acidic type of metalloid element such as phosphorous is used in the formation of the ester (or acyl) product, followed by introduction of two hydrogen equivalents of a divalent metal substituent in accordance with Equation (a) above, metal substitution of OH and also N-substitution with both metal and an acyl group results with probable formation of a metal chelate or metal ring type compound as indicated by the following generalized equation:

and wherein the ring nucleus represent mono or polycyclic aromatic nuclei where Me indicates a divalent metal atom. The broad class of metalchelate compounds is described by Diehl in Chemical Review, vol. 31, page 39 (1937).

Other examples of acyl chlorides of the inorganic acids of non-metallic or acidic metalloid elements that may be used in the N-esterification (acylation) reaction described above are the following: BC13, SiCl4, PCla, SO12, SeClz, Tech, as well as the corresponding bromides and iodides.

In general, as previously indicated, any acyl chloride or anhydride of an inorganic acid may be employed in the esterificaticn or acylation reaction which forms an N-esterifled (acylated) reaction product which is substantially stable toward mineral oils when intimately admixed therewith.

Representative examples of the organic acid anhydrides or acyl halides which may be used for this purpose are the anhydrides and acyl halides of the following organic acids:

(1) Saturated aliphatic mono carboxylic acids ranging from acetic to montanic acid.

(2) Unsaturated aliphatic monocarboxylic acids such as acrylic, oleic, elaidic, crotonic, etc.

(3) Saturated aliphatic polycarboxylic acids such as succinic, oxalic, adipic, sebacic, etc. acids such as succinic, oxalic, adipic, sebacic, etc.

l 4) Unsaturated aliphatic polycarboxylic acids such as maleic and fumaric acids.

(5) Substituted mono and-polycarboxylic aliphatic acids containing halogen, hydroxyl, amino, ether or keto groups such as chloracetic. acid,

octyloxyacetic acid and pyroracemic acid.

(6) Aromatic monocarboxylic acids such as benzoic and naphthoic acids. a

(7) Aromatic polycarboxylic acids such as .phthalic acid.

g (8) Alkylene-substituted aromatic monocarboxylic acids such as cinnamic acid.

(9) Aryl substituted mono and polycarboxylic aliphatic acids with carboxyl in the side chain such as phenylstearic, naphthyl stearic and naphthyl polystearic acids.

(10) Substituted aromatic mono and polycarboxylic acids containing halogen, hydroxyl. amino, alkyl, aryl, aralkyl, keto, nitro, or alkoxy in the nucleus, such as chlorbenzoic, salcylic, anthranilic, toluic, phenyl-benzoic, benzoylbenzoic, nitrobenzoic and anislc acid.

(11) Non benzenoid cyclic mono and polycarboxylic acids such as abietic-and camphoric acids, and heterocyclic carboxylic acids such as furoic acid.

Of the above organic acylating agents, those corresponding to the saturated aliphatic and aromatic acids are preferred. In most cases, compounds of higher V. I. can be prepared by use of the dibasic acid chlorides because of the formation of more resinous products thereby.

It will be understood, of course, that the metal chelate type of compounds described above are not limited to divalent metals but may include R eke, R R Q L Q metals of a valence of one '(such as silver). two, three, four, and live, and probably also six and seven. In the case of mono'valent metals secondary valences come into play in forming the metal-containing ring, such secondary valence forming the linkage or bond between the metal and the nitrogen of the amino group. Such secondary valences also may come into play in forming certain types of metal-chelate compounds in which the metal is poly-valent as will be readily understood by those skilled in the art. The structural formulae and methods of formation of these secondary metal-valence compounds as well as those involving only primary valences will also be readily understood by those skilled in the art from the illustrative general equation and general formulae given above. All the foregoing types of metal-containing compounds, including the non-chelate as well as chelate types, are contemplated by the present invention as oil-improving agents.

Also while the present invention is directed primarily to the above mentioned metal-containing compounds, it is also directed to, and is considered by us to be inclusive of the closely related corresponding metal-free nuclear alkylated acylamino-hydroxyaromatic compounds in which one or both the replaceable hydrogens of the NH: group has been replaced with an acyl (ester) group, preferably the acyl radical of an oxy-acid of phosphorous. Such metal-free acyl-amino compounds may be prepared by omitting the treatment with metal as indicated in general Equation b above, it being understood, of course, that any other desired inorganic acyl-halide or organic carboxyl acid anhydride may be used in place of POCla, although the latter is preferred, and that when an acylated hydroxy group is also desired (which is preferred), an additional equivalent of acyl halide or acid anhydride must be employed over and above that which may be required to acylate the amino group containing replaceable hydrogen, such amino groups, as is well known, being more easily acylated than the hydroxyl group. When one mole of the alkylated amino-hydroxyaromatic compound is reacted with one mole of an inorganic acyl tri-chloride (or other halide) such as P0013, a chelate type compound results in which the side ring or chelate ring contains the negative element of socalled acidic metalloid in place of the metal in the metal-chelate type compound, as illustrated in the reaction represented by the following exemplary equation:

understood by those skilled in the art.

It is generally believed by those skilled in the art that in the formation of any of the above chelate-type compounds the H and amino groups must be in adjacent positions such as the ortho position.

In the formation of the nuclear alkylated amino and substituted amino aryL-metal oxides (phenates) inaccordance with the general reaction represented by Equation a above, the metals are reacted in most instances in the form of metal alcoholates such as metal butylates, the alcohol being regenerated in the reaction. In the case of alkali metal alcoholates, these may conveniently be prepared by reacting the desired alkali metal with a suitable alcohol. In the case of the alcoholates of the other metals, these may most conveniently be prepared from the alcohol-soluble salts (such as alcohol-soluble chlorides or alcoholsoluble acetates and the like) by double decomposition with an alkali metal alcoholate, preferably sodium or-potassium alcoholate. The formation of the alkali-metal alcoholate and the double decomposition may be carried out in separate steps or simultaneously in the same reaction mixture as illustrated I by the following example:

- EXAMPLE III Reaction mixture for formation of stannous salt of C-amyl aminophenol Amyl aminophenol hydrochloride mol '1 Sodium metal do 3 N-butyl alcohol cc" 500 Stannous chloride "(anhy.) mol 1 The sodium is added to the butyl alcohol at reflux temperature to form sodium butylate, to which is added the anhydrous stannous chloride dissolved in butyl alcohol. ,To this mixture is then added the solid amyl aminophenol hydrochloride.

In the reaction, one equivalent of sodium is required to'neutralize the hydrochloride, thereby releasing the free aminophenol whichthen reacts with the stannous butylate formed by double decomposition.

As an alternative procedure, which is more convenient to carry out, the aminophenol hydrochloride can be added to the stannous chloride dissolved in alcohol, followed by the gradual addition of the metallic sodium or sodium butylate.

In either method of mixing the reactants, the reaction temperature is then raised to l'75-200 C. allowing the alcohol to distill, holding the temperature in this range about one hour to complete the reaction. I

Upon cooling, 1 part of benzol is added to the mixture, which can be filtered to remove the reaction salts and the solvent removed to give the finished product. It is desirable to prepare a concentrated blend of the product containing about one part of the metal salt to- 3 parts of a mineral oil, in which case the mineral oil is added during the process of formation of the metal salt and allowed to remain in the finished product.

Some of the metal salts are more stable than others to water-washing. aminophenol salts of tin, cobalt and nickel have been found to decompose to some extent, losing about one equivalent a of metal upon water-washing. Salts of chromium and titanium have been found to be completely stable upon water-washing.

The metal salts are formed in anhydrous medium, but can be water-washed in the removal of reaction salts in the purification of the compounds.

PREPARATION OF METAL SALTS OF WAX- SUBSTI'I'UTED AMINO-AND SUBSTITUTED ANIINO-HYDROXYAROMATIC COM- POUNDS.

(l) Alkylation of phenol with petroleum war A parailin wax melting at approximately F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules is melted and heated to about 200 F,

after which chlorine is bubbled therethrough until the wax has absorbed about sixteen per cent of chlorine, such product having an average composition between -a monochlor wax and dichlor wax. Preferably the chlorination is continued until about one-sixth the weight of the chlorwax" formed is chlorine. A quantity of chlorwax thus obtained, containing three atomic proportions of chlorine, is heated to a temperature varying from just above its melting point to not over F., and one mole of phenol (CsHsOH) is admixed therewith. Themixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to about three per cent of the weight of chlorwax in the mixture is slowly added to the mixture with active stirring. The rate of addition of the aluminum. chloride should be sufliciently slow to avoid violent foaming, and during such addition the temperature should be held at about 150 F. After the aluminum chloride has been added, the temperature of the mixture may be increased slowly over a period of from fifteen to twenty-five minutes to a temperature of about 250 F. and then should be more slowly increased to about 350 F. To control the evolution of HCl gas the temperature of the mixture is preferably raised from 250 F. to 350 F. at a rate of approximately one degree per minute, the whole heating operation occupying approximately two hours from the time of adding the aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached the mixture may be held at 350 F. for

a short time to allow completion of the reaction. But, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extended length of time.

It is important that all unreacted or nonalkylated hydroxyaromatic material (phenol) remaining after the alkylationv reaction be removed. Such removal can beeifected generally by water-washing, but it is preferable to treat the water-washed product with"'super-heated steam,

thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtained may be characterized by the general formula A wax-substituted phenol prepared according to the above procedure, in which a quantity of chlorwax containing three atomic proportions of chlorine (sixteen per cent chlorine in the chlorwax) is reacted with one mole of phenol, may, for brevity herein, be designated as wax phenol (346). Parenthetical expressions of this type (A-B) will be used hereinafter in connection with the alkylated hydroxyaromatic compounds to designate (A) the number of atomic proportions of chlorine in chlor-aliphatic material reacted with one mole of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B) the chlorine content of the'chlor-aliphatic material. In the above example A=3 and 3:16. This same designation will also apply to the metal oxides derived i'rom these alkylated hydroxyaromatic compounds.

Wax-phenol (3-16) as obtained by the above procedure had a phenol content or a "phenolic ratio of about thirteen per cent. Our research indicates that this phenolic ratio of thirteen per cent may be considered as representing about the maximum for satisfactory miscibility and multifunctional activity in viscous oils of the aminoor substituted amino-aryl metal oxides in which the alkyl substituent is derived from wax and the hydroxyaromatic and constituent is derived from phenol (C6H5OH)- (2) INTRODUCTION OF. AMINO AND SUB- STITUTED AMINO GROUPS INTO WAX- SUBSTI'I'UTED HYDROXYAROMATIC COM- POUNDS (a) Introduction of amino groups I compound aminophenol. These variations consist mainly in the use of a suitable solvent or diluent for the wax-substituted compound and other minor variations such as the use of zinc dust as reducing agent which willbe readily understood, by those skilled in the art, from the following example of the nitration step only of wax-substituted phenol:

EXAMPLE IV Nitration 0] was: phenols REACTION mrx'runm v Wax phenol (3-16, 13.7% combined phenol) (1 equiv.) g Stoddard solvent c.'c;.. 100'" NaNO: .(2 equivalents) g-- 25 Water c c..- 60 Cone. H2804 g 31 Procedure The sodium nitrate is dissolved in water and acidified with the cone. H2804, cooling to F. and adding'thereto the wax phenol dissolved in the Stoddard solvent. The temperature is allowed to rise to -160" F. during a one-hour period and then raised to 200 F. to complete the reaction. The mixture is cooled and all traces of acid removed by water-washing, thereafter removing the Stoddard solvent diluent to obtain the 'nitrated product.

The reduction of the nitro group of the end product of Example IV above may be carried out as already stated in accordance with the reduction method of Example II with use of a solvent and other variations similar to those indicated in Example III.

INTRODUCTION OF. SUBSTITUTED AMINO GROUPS INTO NUCLEAR WAX-SUBSTI- T U TE D AM I N O-HYDROXYAROMATIC COMPOUNDS 1 After introduction of an unsubstituted amino group (NH2) into the nuclear wax-substituted hydroxyaromatic compounds by nitration and reduction as described above the unsubstituted amino group may be N-substituted with alkyi,

aralkyl or acyl (ester) groups as previously de-' scribed.

(3) FORMATION OF METAL SALTS OF NU- CLEAR WAX-SUBSTITUTED AMINO- AND SUBSTITUTED AMINO-HYDROXYARO- MA'I'IC COMPOUNDS The substitution of the'hydroxyl and amino hydrogen of the nuclear wax-substituted aminoor substituted amino-hydroxyaromatic compound or product with its equivalent weight of metal may be affected in various ways of which the following are illustrative examples.

EXAMPLE A (a) 500 parts byweight wax-amino phenol (13.2% combined phenol). 16 parts by weight of sodium in the form of alkyl sodium oxide; or equivalent amount of other alkali alcoholates. (b) 500 parts by weight of wax-phenol (13.2%

combined phenol). 14 parts by weight of calcium in form of alkyl calcium oxide or equivalent amount of other alkaline earth metal alcoholate.

In forming the alkyl-substituted amino-aryl oxides of the metals other than alkali metals through the use of alcoholates of such metals, the preferred procedure is to first form the alkyl oxides (alcoholates) of such metals by double decomposition of alkyl sodium oxide with an alcohol-soluble salt (such as a chloride acetate, or the like) of the desired metal. The alkyl(wax) substituted amino hydroxyaromatic compound is then added to the alkyl metal oxide mixture without separating. the pure alkyl oxide of the desired metal from the alkali salt, and the mixture is heated during one hour at 400 F., allowing the alcohol to distill to complete the formation of the nuclear alkyl-substituted amino aryl oxide of the desired metal. The reaction product is then purified by diluting the mixture with a light mineral oil to aid the separation of the alkali salt, which is removed by settling, filtering or centrifuging, after which the diluent is distilled to obtain the finished product.

ADDITIONAL EXAMPLES By the use of difierent metal salts and by varying the proportion of reactants as will-be understood from the above by those skilled in the art, the following compounds have been prepared:

, The conversion of wax-amino hydroxyaromatic compounds to wax-amino-aryl metal oxides results in considerable increase in viscosity with the formation of tough and waxy materials. With an increase in metal content the tendency is toward the formation of a rubber-like product, and

on this account it is often desirable to use diluents in the preparation of the compounds for the purpose of reducing the viscosity of the mixtures. In the event the compounds are being prepared for incorporation in a particular oil it is convenient to employ as a diluent a quantity aasopsa in this reaction. Illustrative reacting proportions are:

metal oxides should be of relatively high molecular weight. In order to obtain compounds having pour depressantand viscosity index improving properties along with other improved properties, such as sludge inhibition, etc., we have found that the alkyl substituents should preferably be in the nature of petroleum wax or in aliphatic hydro-carbon of correspondingly high molecular weight, and for that reason the wax-substituted compounds are considered preferable for the purpose of this invention. Although the wax-substituted products are considered preferable for the reasons just stated, oil-miscible alkyl-substituted amino aryl metal oxides may be prepared from alkylated amino-hydroxyaromatic compounds in which the alkyl substituent is de 'rived from Transil oil '(a (highly'refined viscous parafdn base white oil having a Saybolt viscosity of. eighty-two seconds at 100 F. and specific gravity of 0.8498) and from tertiary amyl-amino phenol.

As will appear from the foregoing description, the oil-improving agents contemplated by this V invention are characterized by the general of the same oil with which the compounds are to I Formula III R"(T(0M) (N')Yb)n described hereinabove; such chemical compounds or products may also be characterized as oil-miscible alkylated or alkyl-substituted amino-aryl metal oxides or alkylated amino-hydroxyaromatic compounds in which the hydroxyl and preferably also the amino hydrogens have been replaced with their equivalent weights of metal," it being understood that the term alkyl and alkylated are used herein in a broad sense to include polyatomic or polyvalent, as well as monovalent aliphatic radicals or groups and also that the term amino is inclusive of substituted amino groups.

While the preferred method of preparing the alkylated amino-hydroxyaromatic compounds (in which the amino group is unsubstituted) is the nitration and reduction of the corresponding alkylated compound as described above, other methods may be employed for this purpose as follows:

' (1) By reduction of alkylated nitroso-hydroxy- I aromatic compounds (isomeric with quinone monoximes) with the above reagents.

(2) By coupling alkylated hydroxyaromatic compounds with benzene diazonium chloride and subsequent reduction 'as above.

(3) By electrolytic reduction of alkylated nitro aromatic compounds.

(4) By reduction of alkylated nitro-hydroxyaromatic compounds with hydrogen in the presence of a catalyst.

For the formation of.- the alkylated polycyclic compounds such as amino-naphthols, procedure (2) above is the preferred method.

As will be noted, each of these methods is carried out after alkylation of the aromatic starting material. In method (3), as is well known to those skilled in the art, the aromatic nitro compound is first reduced to aryl hydroxyl amine which under the conditions undergoes molecular rearrangement "into the, corresponding aminohydroxyaromatic compound.

SOLUBILITY OF THE METAL SALTS OF- ALKYLATED AIMINO- AND SUBSTITUTED AMINO-PHENOLS IN IVIINERAL OILS Metal salts of the above compounds can be solubilized in mineral oils when prepared from aminophenols containing C-alkyl substituents. An isoamyl substituent or a wax radical has been 2,280,039 i found necessary to give the desired solubility.

Substituents such as C-alkoxy or organic ester groups or N- alkyl, aralkyl or ester groups have solubilizing value, but are not desirable without C-alkyl substituents being present..

C-alkyl substituents are preferred to N-alkyl substituents not only for solubilizing value, but because of the readiness of preparation and the eifectiveness of metal or acyl metalloid derivatives prepared therefrom.

To demonstrate the effectiveness of compounds or products of the type described above in the mineral oil compositions contemplated by this invention, we have conducted several comparative tests, the results of which are listed below, with representative mineral oils alone and with the same oils blended with various representative alkylated amino-aryl metal oxides.

POUR TEST This series of tests was conducted with a mineral lubricating oil fraction having a Saybolt viscosity of 44.9 seconds at 210 F. and an A. S. T. M. pour point of 120 F. The alkyl-substituted amino-aryl metal oxides used were derived from wax-substituted phenolic compounds obtained by condensing chlorwax of substantially sixteen per cent chlorine with the phenolic compound in the ratio of one molecular proportion of phenolic compound to a quantity of chlorwax containing three atomic proportions of chlorine, this condensation product being indicated by (3-16) in Table I below. The aryl constituents of the compounds used in these tests were phenol.

The compounds obtained from phenol are listed in the table as the corresponding metal salts of wax amino-phenol. The results of these tests are listed below.

TABLE I Action of metal salts of wax-aminophenols a pour point depressants comparative behavior of the unblended oil and the improved oil compositions under actual operating conditions. This test was carried out in a single cylinder CFR. engine cooled with a dlethylene glycol-water mixture held at a temperature of about 390 F. The engine was operated continuously over a time interval of twentyeight hours at a speed of about 1200 R. P. M., which is equivalent to a road speed of about twenty-five miles per hour. The oil temperature was held at about 150 F. during the test.

The conditions observed at the end of the test were (a) the extent to which the piston rings were stuck, (b) the extent to which the slots in the oil rings were filled with deposit, (0) the amount of carbonaceous deposits in the oil, and

(d) the neutralization number (acidity) of the oil at the end of the test. The oil used was a lubricating oil stock of 120 seconds Saybolt Universal viscosity at 210 F. and the results, which are recorded in Table II below, show a marked improvement in mineral oil compositions of the type contemplated by this invention over the oil alone.

In running these tests comparative runs were made with a sample of the blank oil for each sample of ofl containing the addition agent. In Table II below these blank oil samples are indicated by A1, A2, etc,.. and oils with addition agents used in the corresponding runs are indicated by B1, 132, etc. These last-mentioned oil blends as set forth in Table II below contained the following addition agents in the amounts indicated:

TABLE II Action of metal salts of alkylated aminophenols as inhibitors in C. F. R. ring test (28 hours) A. S. T. M. pour test Improving agent Stannous-phenate-stannous aminate F. F. F. F.

of wax-aminophenol 3-16) +20 10 20 25 Cobaltous phenate-co altous aminate oi wax-amino henoi (ii-16)..-. +20 +10 5 l5 stannous henateo wax-aminophe- :10] (3-16 +20 -10 20 Cobaltous henate oi wax-aminopheno1(3-l6 +20 10 20 Chromic phenate-chromic animate oi'wax-aminophenol (316) +20 5 20 Stamens phenate-silicon amide oi wax-aminophenol (3-16) +20 10 20 Silicon amide of wax-aminophenol (3-16) +20 5 l5 Phosphite ester of phosphite amide of wax-aminophenol (3-16) +20 5 20 From the foregoing results it will be observed that the alkyl-substituted amino-aryl metal oxides contemplated by this invention, when present in a mineral lubricating oil in amounts as small as one-eighth of one per cent, are effective in depressing the pour point of the oil by a substantial amount. At higher percentages up to the depression of the pour point is considerably greater, as clearly shown.

OPERATION TEST Ring condition Percent slots Grams Oil Degrees stuck fined carbon N. N

deposit A1.... 360 360 360 360 360 90 90 90 17. 3 1.1 B1. 0 0 0 0 0 0 0 0 5 3 0. 6 A2- 270 360 360 360 360 80 60 15. 3 l. 6 B2. 150 0 0 0 0 0 0 0 4. 6 0. 6 A3. 360 360 360 360 360 80 80 16. 2 3. 0 Ba. 0 0 0 0 0 0 0 0 4. 8 0. 7 A4" 330 360 360 360 360 80 70 60 14. 7 2. 8 Bi. 0 0 0 0 0 0 0 0 3. 1 l. 4 At 360 240 360 360 360 80 90 60 17.9 2.8 BL 0 0 0 0 0 70 70 70 14. 9 0. 6 Au- 270 0 360 360 360 70 70 50 16. 1 2. 5 Ba. 0 O 0 0 0 10 10 5 8. l l. 2

The improvement produced by the improving agents of the present invention in the viscosity index of mineral oils to which they are added is clearly shown by the illustrative data in the following table:

TABLE 111 Action of wam-aminophenols and metal salts thereof as viscosity index improvers S. U. V. at*

Compound 332 1 V. 1.

None o 134. a 41. 6 s5. Stannous henate oi wax-amino- 1 155. 43. 97. My phenol 3-16) 2 181. 6 46.0 109. -Gobaltous phenate oi wax-amino- 1 148. 6 42. 8 92. stghenol (3f! 16)---t-----t d5- 2 165. 4 44.0 94. nnous p ena e-s anno laminate oi wax-ammophenol 3g 1 0 l Cobaltous pbenate-cobaltous 123mir$ite 0t wax-aminophenol i vanad l'iviiii'i-Vifiak'if "1511 1 151. 7 42.9 90. note 01 wax aminophenol(3l6) .2 172. 2 44. 4 93. Phosphorus amide of wax-ami- 1 145.4 42.6 93. stzoo-phenol -1s) 2 157.0 43.8 101.

annous p ena e-p osp orus of wax-aminophenol 3 ag: Pum ed-K511311111; Kr'bfifiiiit 2 150. 4 42.6 an. ester of wax-ammophenol (3-16) 1 162. l 43. 6 90. Silicon amide oi wax-amino- 1 143. 8 42. 6 94. phenol (3-16). 2 153. s 13. 1 104. Stannous phenate-slhcon amide 1 143.8 42.6 94. Cgf wax-aminolphentol (Iii-19 n" 2 175. 6 45. 0 103.

romium p ena e-c rommm agiiiite oi wax-sminophenol gzg The improvement produced by the improving agents of the present invention when blended with turbine oil, with respect to color stabilization and acid formation, is shown by the illustrative data in Table IV below. In obtaining this data, the behavior of the turbine oil both with and without the improving agent was observed under conditions approximating those present in the actual use of such oils and involved the use of 25 cc. samples of'the oil or oil blend. Each sample contained 1 gram of iron granules and 24 inches of 18 gauge c pper wire and was heated to a temperature of 200 F. with 5 liters of air per hour bubbling therethrough. During each test 2 cc. of distilled water were addedeach day. The samples were tested for color and acidity or neutralization number (N. N.) at various time intervals, the results being embodied in the following table.

TABLE IV Socony-Vacuum turbine test (200 F.)

Compound blended with R0- Conc b Time y I Color g'es1s&%0.(Say. ms. of 155 sec. Weight hlilrs Low. N. N.

Chromium salt of amyl aminophenol (chromium metal, Percent v 23.0%) 0.1 162 a. 5 0.01 330 4 0.02 546 2. 5 0. 02 1, 003 4 0. 01 1, 484 3. 1 Stannous salt of amyl aminophenol (tin metal, 31.3%) 0. 1 167 4 0.01 330 3 0. 01 449 2. 2- 0. 01 1, 003 2. 6 0. 05 l, 152 14. 0 8. 8 None 44 2. 4 0. 32

In Table V below, illustrative data are pre- Hi QHOHNCJ -10 OMOlioar- -19 manor-no of the specified motor tuel (Ellis gas from pregrey tar distillate) or a blend of the same with the different specified improving agents or inhibitors was introduced in a pressure bomb and the bomb was charged with 10012 lbs. of oxygen. The charged bomb was then immersed in a boiling water bath. The pressure within the bomb then rises to a maximum and continues atthat maximum until the motor fuel begins to absorb to initiate a reaction between the motor fuel and oxygen under specified conditions. In making the tests shown in Table V below, 100 ml.

the oxygen, whereupon the pressure decreases. The induction period of the motor fuel is measured in hours beginning at the time the bomb is immersed in the water bath and continuing until absorption of oxygen is noted by a decrease of pressure. The illustrative data thus obtained is shown in the following table.

TABLE V Oxidation bomb test It will be apparent from the foregoing description that we have developed a new class of mineral oil compositions characterized by the presence in a minor proportion of an alkyl-substituted amino-arylmetal oxide as an improving agent. The improved propertiesobtained and the degree of improvement effected in a particular property may be varied with the metal substituents and the aryl constituents in the oxides; also by the degree'of alkylation- .of the aryl nucleus. As to the degree of alkylation, it is important that the aryl nucleus be sufliciently alkylated to provide a final product which is soluble" or miscible in the particular mineral oil fraction with which it is to be blended; that is, one which will remain uniformly dispersed in the oil in sufiicient amount to effect the desired improvement. Thepresent joint inventors, Ser. No. 206,683, filed May 7, '1938 now issued as Patent No. 2,197,833 of April 23, 1940, there is disclosed and claimed an alkvlated aryl metal oxide containing a nuclear unsubstituted amino (NH2) group as an optional nuclear substituent among other likewise optional nuclear substituents, whereas the present application discloses and claims broadly both substituted and unsubstituted amino groups as an essential or characterizing class or group of nuclear substituents, having an active influence upon the properties of the improving agent of irom the above data it is seen that the introduction of metal substituents into alkylated .aminophenols influences greatly the action of the compounds as addition agents for lubricating oils and gasolines. Whereas the stabilization of motor oils against ring-sticking, acid formation and viscosity increase is a property common to most metals, although to a varying degree, the stabilization of turbine oils and gasolines by the addition of these metalorganic compounds is highly selective; I

For use in motor oils, cobalt is superior to other metals tested to date as a substituent. for alkylated aminophenols. For use in turbine oils, tin and chromium are outstanding as oxidation inhibitors. I For use in gasolines, tin has been found to be the most effective metal substituent.

' It is to be understood that while we have described certain preferred procedures which may be followed in the preparation of the alkylated amino-aryl metal oxides used as improving agents in the mineral oil compositions contemplated by this invention and have referred to various representative constituents in these improving compounds, such procedures and examples have been used for illustrative purposes only. The invention, therefore, is not to be considered as limited by the specific examples given but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

I claim:

1. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkylated amino-aryl metal oxide.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith a. minor proportion of an oil-miscible aminoaryl metal oxide in which part of the nuclear hydrogen has been substituted with predominantly aliphatic organic material, said last-mentioned substituent comprising a suflicient proportion of the amino-aryl metal oxide to render same misciprising a mineral oil having admixed therewith a minor proportion of an oil-miscible nuclear alkyl-substitu'ted amino-aryl metal oxide in which the nuclear alkyl substituent is a high molecular weight aliphatic hydrocarbon derivative.

6. An improved mineral oil composition comprising a mineral voil having admixed therewith a minor proportion of an oil-miscible nuclear a1- kyl-substituted amino-aryl metal oxide in which the nuclear alkyl substituent is derived from an aliphatic hydrocarbon having at least twenty carbon atoms.

7. An improved mineral oil composition comprising a mineral oil having admixed therewith' a minor proportion of an oil-miscible nuclear which the alkyl substituent is derived from petroleum wax.

8. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible nuclear substituted amino-aryl metal oxide in which the substituent is a high molecular weight aliphatic hydrocarbon group and in which the aryl nucleus is poly-substituted with said substituent.

9. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible substituted amino-aryl metal oxide, in which the substituent is derived from an aliphatic hydrocarbon having at least twenty carbon atoms and in which the aryl nucleus is poly-substituted with said aliphatic derivative.

10. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible nuclear substituted amino-aryl metal oxide in which the substituent is derived from petroleum wax and in which the aryl nucleus is poly-substituted with said wax derivative.

11. An improved mineral oil composition com: prising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted metal amino-phenate.

12. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted-metal amino-naphtholate.

13. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted metal amino-phenate in which the alkyl substituent is a high molecular weight aliphatic hydrocarbon derivative.

14. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted metal amino-naphtholate in which the alkyl substituent is a high molecular weight alialkyl-substituted amino-aryl metal oxide in phatic hydrocarbon derivative.

15. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted metal amino-phenate in which the alkyl substituent is a high molecular weight aliphatic hydrocarbon derivative and in which the aryl' nucleus is poly-substituted with said aliphatic derivative.

16. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted metal amino-naphtholate in which the alkyl substituent is a high molecular weight aliphatic hydrocarbon derivative and in which the aryl nucleus is poly-substituted with said aliphatic derivative.

17. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible wax-substituted metal amino-phenate.

18. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible wax-sub-- stituted metal aminonaphtholate.

. 19 An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible alkyl-substituted amino-aryl metal oxide in which the metal substituent is selected from the group consisting of tin, chromium, cobalt, and titanium.

20. An improved mineral oil composition comof said'metal.

prising a mineral oil having admixed therewith a minor proportion'oi a nuclear alkylated aminophenol in which hydroxyl hydrogen has been replaced by its equivalent weight of metal and in which the alkyl substituent is derived from pctroleum wax, the proportion by weight of phenol in the nuclear alkylated amino=phenol constitu= ent being in the neighborhood of about thirteen per cent.

21. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible nuclear alkylated amino-hydroxyaromatic compound in which the hydroxyl hydrogen has been replaced by its equivalent weight of metal and in which the proportion by weight of the hydroxyaromatic constituent in said alkylated-amino-hydroxyaromatic constituent is chemically equivalent to not more than sixty per cent phenol.

22. An improved mineral oil composition comprising a mineral-oil having admixed therewith a minor proportion of an oil-miscible alkylated amino-hydroxyaromatic compound in which the hydroxyl hydrogen has been replaced with its equivalent weight of metal and in which the proportion by weight of the hydroxyaromatic constituent in said 'alkylated=amino=hydroxyaro= matig constituent is chemically equivalent to not more than seventeen per cent phenol.

' 23. An improved mineral oil composition comprising a mineral oil having admixed therewithsubstitutingthe hydroxyl hydrogen with a metal toform a wax substitutedamino-aryl metal oxide 24. Anlmproved' mineral oil composition comprisinga viscous mineral oil fraction having admixed therewith a minor proportion, from about one-sixteenth per cent to about five per cent of an oil-miscible nuclear alkyl-substituted aminoaryl metal oxide in. which the alkyl substituent is derived from an aliphatic. hydrocarbon, having, at least twenty carbon atoms.

26. An improved mineral oil composition comprising av viscous mineral oil fraction having 'ad,- mixed therewith a'minor proportion, from about one-sixteenth per centto about five per cent of an oil-miscible nuclear alkyl-substituted aminoaryl metal oxide in which the alkyl substituent is derived from petroleum wax.

27. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula v in which T represents an aromatic nucleus;

(OM) represents at least one hydroxyl group in its. equivalent weight of a metal, M, said group being attached to the nucleus T: (N') represents a.v monovalent radical selected f om the group consisting of alkyl amino. arauryl amino, acyl amino (ester), and metal amino radicals; R represents at leastone aliphatic group having a valence v of one to 1 ur, and attached by one valence only to at least one nucleus T; Y represents a monovalent radical selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, nitroso, diazo, azo, keto, ether alcohol and ester radicals; b represents the number of Y's.

and is equal to zero or a whole number corre- R"(T(OM) (Norm);

in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of metal M, said group being attached to the nucleus T; (N') represents a monovalent radical selected from the group consisting of alkyl amino, aralkyi amino, acyl amino (ester), and metal amino radicals;.R represents at least one aliphatic group having a valence 'v of one'to four and attached by one valence only to at least one nucleus T; Y represents a monovalent radical selected from the group consisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, aryl, nitro, nitroso, diazo, azo, keto, ether alcohol and ester radicals; b represents the number of Y's and is equal to zero or a whole number corresponding to the valences on 1 the nucleus T not satisfied by R", (N') or (OM) and n is a whole number from one to four; the total number of carbon atoms in all of the aliphatic groups taken together in said metalorganic compound being not less than about thirty for each nucleus T.

29. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in. which the hydroxyl, hydrogen is replaced with its equivalent weight of metal M, said group being attached to the nucleus T; (N') represents a monovalent radical selected from the group equal to zeroor a whole number 'coresponding to which the hydroxyl hydrogen is replaced with the valences on the nucleus T not satisfied by R (N') or (OM) and n is a whole number irom one to four; the equivalent ratio of T(OH) to R"(T(OH) )1: in said metalorganic compound being not greater than the chemical equivalent of seventeen per cent phenol.

30. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula (N') represents a 15 group of at least twenty carbon atoms having a 20 valence v of from two to four; Yb represents a monovalent radical selected from the group consisting of residual hydrogen, chlorine, alkoxy, aroxy, alkaryl, aralkyl, aryl, nitro, nitroso, diazo, azo, lgeto, ether alcohol and ester radicals; b represents the number of Ybs and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R (N'), (OM), and Re; Re represents monovalent aliphatic radicals; 0 represents the number of Rcs and is equal to zero or a whole number corre sponding to the valences on the nucleus T not satisfied by R'', (N'), (OM). and Ye; and n is a whole number from two to four.

31. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a stannous phenate-stannous aminate of wax amino-phenol.

ORLAND M. REIFF. HOWARD D. HARTQUGH.

CERTI FICATE OF C ORREC II ON t Patent No. 2,280,059.}

April it, 192 2..

QRLAND H. REIFF, ET AL.

- It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 25, for "We" read --R's--; page 6 first column, line 65 .for-

thallium read --.thu1ium--;

page 9, first column, line 70, strike out the "words "acids such as succinic, oxalic, adipic, sebacicg etc."; "page 10, first column, line 25 before the equation, insert '-(c)--; page 114;, first column Table III, second column thereof, opposite "Phosphorus amide of phosphite ester of wax-aminophenol (3-16)", for

and that the said Letters Patentshould be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of July, A. n. 1915.

(Soul)- Henry Van Arsdale', Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION, Patent No. 2,280,039J' April 1h, 19 2 0mm) 11. REIFF, ET AL.

It is hereby certified that error appears in the printed specification ozi. the above numbered patent requiring correction as follows: Page 5, first column, line 25, for "We" read --R's--; page 6 first column, line 65, .for "thullium" read --e thu1ium--; page 9, first column, line 70, strike out the "words "acids such as euccinic, oxalic, adipic, sebacio; etc."; "page 10, first column, line 25, before the equation, insert '--(c)--; page 11p, first column; Table III, second column thereof, opposite "Phosphorus amide of phosphite ester of wax-aminophenol (3-16)", for

read 1 and that thesaid Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed ind sealed this 6111 day of July, A. D. 191;

Henry Van Arsdale', (Sea1)- Acting Commissioner of Patents. 

